Indigoid coloring compounds



Patented Apr. 9, 1946 J .2,397,9zs

Joseph B. Dickey and James G. McNally, Rochester, N. Y., assignors toEastman KodakCompany, Rochester, N. 1%, a corporation of New Jersey noDrawing. Application May 9.1940. V p Sjerial No. 334,236 I a .5-Claims..01. zeo eze) This invention relates to'indi'goidcoloring, mat terscontaining. an acid ester of anf acidof phosphorus. group. and their.application to the coloration. of materials. More particularly our.inven tion relates to water-soluble. indigo and thioindigo dye.compounds. containing an acid ester of an acid of phosphorus. group.and; their application for. the colorationoi. textile. materials,especially organic derivatives. of cellulose. by dyeing, printing,stenciling. or likefmethods.

Ind-igoid. coloring; matters. are characterized, by the presence of.the. chromophore. CO.C:C.CO. While our invention relates broadly tqdye;compounds containing. this chromophore groupingfit relates more.particularly to: theindigo.- and. thio: indigoinembers oithe series.Further while our invention. relates. broadly to. an: acid ester oi anacid: of phosphorus grouping it. relates more particularly tosuch agrouping. which the phosphoric or phosphorusgroupcontains a substituentsuchasan: alkyl, 5, phenyha cyeloalkyl, a turyl an aralkyl or anaminogroup. I

It is an: object. of our invention. toprovide new indigoidcoloringmatters. Another objector our invention is to provide watersoluble indigoid coloring matters containingv an acid ester or an acidof phosphorus group: A. further object is to provide: newwater solubleindigo andthioindigo dye compounds containing an. a oid ester ofan acidof phosphorus group. 'A still. further object; is to provide coloredorganic derivative of cellulose textile; materials which: are .of good;fastness. to light and washing. Other objects will; appear hereinafter.

In order that the expression organic. derivatives of cellulose may be;clearly understood, it should be noted that typical organic derivativesof cellulose include the hydrolyzed as well as the unhydrolyzed' organicacid: estersof cellulose, such as cellulose acetate, celluloseformate,'cellulose propionate. or cellulose: butyrate, and'thehydrolyzed as well as the unhyd'rol'yzed mixed organic acid esters ofcellulose such as cellulose acetatepropionate, celluloseacetat'e-butyrateand the cellulose others; such as methyl cellulose,ethyl cellulose or benzyl? cellulose.

The acid ester of an acid'of phosphorus group is joinedindirectlyto-theindigoid' coloring matter. Various linkages. canbeemployed to join the acid ester'of an acid of phosphorus group totheindigoid nucleus. Normally the acid ester of an acid of phosphorus groupis joined through a suitable linkage to a nuclear carbon atom althoughit can be similarly joined to another atom such as a nuclear nitrogenatom for example The acid ester of an acid of phosphorus group, which ismoreparticularly defined hereinafter, is joined through oxygen, carbon,sulfur or nitrogen or a combination of two or more of these elements tothe nucleus of. the indigoid compound.

Ordinarily the acid ester of an acid of phosphorus grouping which weshall sometimes refer to hereinafter as the phosphorus grouping" isjoined through an O-aliphat ic or-a.

l I-alipliatic linkage to the indigoid nucleus. The aliphatic linkagemay be an unsubstituted hydrocarbon linkage containing at least twovcarbon atoms such as --CH2CH2., CH2CHzCH2-,

for example, a substituted hydrocarbon linkage such as .CHiCH2N CH2Ql1nk af d x m le co d i .P m lo e. The 'pho'sphorusgrouping' canfl ewise'be joined to .t ser carbon a o the i i 7 1 phatic linkage, for egample.-Whilethevarious illustrative aliphatic linkages above given can beemployedordiriarily the ethylenelinkage is'used.

The'expr'e'ssion an acid ester ofan acid of phosphorus "includesesters-f for example, of phosphoric, phosphorus and'thiophosphoricacidsv By a phosphoric acid ester group we include the phosphoric acidester group in its free acid,

for example, as well as substituted acid ester groups such as OCH: NH:

o-r=o -o OCH: 0H

OCsHs OCH;

ONHc and , NHI

O CHI .by omitting the double bonded oxyg en atom attached to phosphorusinthe. above formulae given for representative phosphoric acid estergroups. The new indigoid coloring compounds of our invention can ,beprepared by introducing a phosphorus group into an indigoid compoundcontaining an external hydroxyl group capable of being phosphoric Iconverted to a phosphorus group. The agent used to convert the hydroxylgroup into a phosphorus group will be referred to by use as aphosphating agent. Suitable phosphating agents include,for example,phosphorus oxychloride, POCIa, phosphorus oxybromide, POBra, phosphoricacid HaPOa 'iPhQSDhOIiC anhydride; Pz0s',?phosphorus sulfochloride,PSCls, phosphorus sulfobromide, PSBra, phosphorus pentasulfide, P285,phosphorus trichloride, P012, and phenoxyphosphorus dichloride, I

The preparation, of numerous pho'sphating agents 7 which can be employedin the preparation of the new indigoid coloring compounds of ourinvention is described or indicated following the examples illustratingthepreparation of our newindigoid dye compounds. 1 1

The new indigoid oonipoundsof our invention, depending on theirparticular structure, possess affinity for organic derivatives ofcellulose, wool, silk, cotton, viscose, linen, nylon and casein wool.Whether a dye possesses suflicientaffinity for one or more of thesematerials to make it of practical value can be readilydetermined by afew simple dyeing tests. The compounds possess rather general affinityfor organic derlvatives of cellulose, especially cellulose acetate'silk,but this afiinity varies considerably.- Compounds 7' wherein thephosphorus group is unsubstituted appear to have lessaffinity forcellulose acetate silk, for example, than those in which'the phosphorusgroup is substituted. For the dyeing of organic derivatives of cellulosethe dyes should contain no'free sulfonicacid group attached directly toits nucleus. The dye compounds of our invention possess a wide range ofsolubility in water, varying from those practically insoluble orrelatively insoluble I to those having a relatively high solubilityinwater. Many of the compounds are sufliciently water-solublethat theycan be applied directly from an aqueous solution to the material beingdyed or colored without the use of a dispersing'or solubilizing agent.Itshouldbe noted, however,that those compounds havinga relatively highwater solubility have less aflinity for organic derivatives of cellulosethan those not having such a relatively high water solubility. r

The water solubility of the indigoid dye com-. pounds of our inventionis dependent on a variety of factors. The presence of certain saltforming atoms or radicals such as Na, K or NH4 increases the solubilityof' the compounds in water. To illustrate, compounds wherein one or moreof the hydrogen atoms of the phosphorus group arereplaced by an alkalimetal 'suchas sodium or potassium 'or the ammonium radical aremorewatersoluble than the corresponding compoundswherein the hydrogenatoms-are not replaced or are replaced, for example,- with analkyl or anaryl radical. Similarlywhere the phosphorus group is joined to anunsubstituted hydrocarbon-linkage, the solubility generally decreaseswith increase in the number of carbon atoms in the linkage. It will beunderstood that the remarks made with respect to water solubility aremerely illustrative Generally speaking, compounds wherein at least oneof the hydrogen atoms of the phosphorus group is substituted with asubstituent, other: than a salt forming group or radical, are betteradapted for the dyeing-or coloring of organic derivatives of cellulose,such as cellulose acetate, than those in which the hydrogens are notsubstituted or are replaced by a salt forming group or radical.

As previously noted, any of the indigoid coloring matters, constitutinga well known class of dyes, which contain a hydroxyl group, joinedthrough a suitable linkage to the nucleus, capable of being convertedinto a phosphorus compound can be employed in the preparation of the dyecompounds of our invention. Our invention, however, relates moreparticularly to the indigo and thioindigo members of the indigoidseries. Our invention will be clear from the following examples whichillustrate the preparation of the dye compounds of ourinvention.

H HOHzCHzC-N group: toobtain dye compounds. in which: the hydroxyl.groups are replaced by the phosphoric groupingssl'iown.inthe-example;

Example 2' 3-3.2'grams of s p-hydroxyethylamino group isconverted to aare placed in pyridine and. treated in the cold group. The dye compoundobtained in accord ance with the example colors cellulose acetate silkblue.

Example 3 40.2 grams of i t H g c n noHoHoHcHc- Urwomcnonomon 0:0 5/ \Swith 44.7 grams of methoxy phosphorous oxydichloride,

The reaction which takes place is completed by Warming following whichthe reaction mixture obtained is treated with a sodium carbonatesolution to obtain the mono sodium salt form of the dye. In the reactionwhich has taken place, the B-hydroxyethylamino groups attached to theindigo compound are converted to a OCH;

group. If other salts of the compound obtained are desired, the compoundis treated with a mineral acid and then with the desired base as, forexample, ammonia, calcium hydroxide or diethanolamine following whichthe dye compound formed is recovered by salting, filtered and dried. Thedye compounds obtained in accordance with the example color celluloseacetate silk blue from an aqueous solution.

It will be understood that the B-hydroxyethylamino groups of the indigostarting compound can be replaced, for example, by afl-hydroxypropylamino, a

are dissolved in. pyridine and treated in the cold with 30.7 grams ofphosphorus oxychloride and V the reaction which takes place is completedby groups, The dye compound obtained'colors cellulose acetate silkbluish gray.

Example 4 33.5 grams of are dissolved in pyridine and treated with. 38.6grams of H nomcmc- CHaO-CH2GHr-O-P in the cold and the reaction iscompleted by warming. The chloride of the 'dyefor'medlis hydrolyzed bytreatment with aqueousv sodium carbonate following which the reaction"mixture is neutralized with a mineral acid. Following the treatmentdescribed the reaction mixture is then treated with ethanolamine,filtered, and'the dye compound precipitated from the filtrate by theaddition of sodium chloride. The dye compound formed is then recoveredby filtration and dried. In the reaction which takes place thefi-hydroxyethylamino groups are converted to onnmcmcmon groups. The dyecompound of this example colors cellulose acetate silk violet.

Example 5 26;? grams of V uxod mo melon, 01m

Example 6 35 grams of CHaCHzOH (IJHnOHzOH are treated in the cold with34 grams of phosphorus oxychloride, the reaction and recovery of the dyecompound being carried out as described in the previous examples. In thereaction taking place the p-hydroxyethyl groups are"co'nverted to /0Na-CH:CHO-fi o ONa groups. The dye compound obtained colors celluloseacetate silk blue.

By the substitution of an equivalent gram molecular weight ofmethoxyphosphorus ovy-dichloride or an equivalent gram molecular weight ofbenzyloxy phosphorus oxy-dichloride for the phosphorus oxychlori'de ofthe example dye compounds, in which the fi-hydroxethyl groups areconverted to l OCH and CHzCHz-0P V v O ONa groups, can be obtained.

Example 7 38.2 gra s of are treated in pyridine with 32.4 grams of Thereaction and recovery of the dye compound can be carried out inaccordance with the procedure described in the foregoing examples. Inthe reaction which takes place the p-hydroxyethoxy groups are convertedto groups. The dye compound obtained colors cellulose acetate silk blue.

Example 8 .1 gram molecular weight of wherein n represents 1, 2 or 3,for example, is

heated in dimethylaminocyclohexane with .2 gram mol of (phenoxy-,methoxy-, o-tetrahydrofuryl-, benzyl-oxy or cyclohexyl-oxy) phosphorusoxy-dichloride, the reaction being carried out in accordance with theprocedure previously described. In the reaction which takes place thealiphatic groups attached to the indig dye are converted to /ORCH2CHg(OCHzCH2)sO% -0 groups wherein R represents phenyl, rah'ydrofuryl,benzyl or cyclohexyl.

Example 9 ONE 43:9 grams of II C H H NCH OH on Homomcm N-dmcmon methylteta somcae '5 is dissolved in pyridine and treated with 45.4 V Example1 2 grams of phosphorustrichloride in the cold. The 33.8gramsof reactionmixture is then slowly warmed to 6070 C. and held at that temperaturefor one hour {I after which it is permitted to cool, .The sodium H saltof the dye formed is obtained by adding 50- I slightly alkaline tolitmus. The pyridine is rev moved from the reaction mixture bydistillation q 4 followin which the reaction product is dissolved i I inwater, filtered and the desired dye compound reacted pyrldme h -grams of0-tetr,a obtained by precipitation withsodium chloride ihywfmyl The andfiltration. 5m thereaction which takes place e i e Iewvery t y compoundthe 'fi-hydroxyethylarninogroups are converted to earned f as qescrlbedm vEmimples l A l r 15 In the reaction whichtakesplacethe-WhYQ OXY- diumhydroxide until the reaction mixture is V '0Na1 .ethylaminogroupis-convertedtoa ONa p I i H a t t f groups. The dye compound obtainedcolors silk, -C =-Q-:P 7 0 W001, nylon and casein wool blue. Rona v I i7 Example 10 V I group, this groupb'eingjshown'in its sbdiumsalt3852gmms of I l l, form. The dye 'compound'obtainedfyielfis violet I; rY colorations.

Example 13 33:4 grams of I is dissolved in pyridine and reacted with232.1 6 H grams of, phenoxy phosphorus oxy-dichloride.

The reaction and recovery of the dye compound formed can be carried outas described in Ex- 1S 'leacted Wlth 1 83 {111113110X}! D arnple 9. Inthe reaction which takes place the phorus oxy'monochlorlde, thfi 63 9and P glycerylamino group is be lieved to be converted coveryofbfimgfiarmed to a out as described'm Examples 5. to 10. re-

v action which takes place the y-hydroxypropyl 11 l 40(group-is'convertedtoa group-The dyecompdund obtained'colors cellu- Olose acetate silk, wool, nylon and silk blue. group. The dye compoundobtained yields violet Y I: 11 colorations.

' mm? Example 14 401.2 gramsof: 1

mo, cm'omon Y is treated in pyridine with 1 grain mole .of methoxyphosphorus oxy-dichloride, the reaction :and recovery of the dyecompound formed being carried out as described in Examples 1 to 10.

is'diss'olvedin pyridine and treated with "170.6

grams 1' i l 7 In the reaction which takes place the fi-hydroxywe.ethoxy groups are converted to m- -P i l J 00m N (CH1): --O CHaCHz-O-Pll oan in accordance the procedure described in Example '9.In'the-reaction which takes place groups. The dye compound obtainedyields red the p-"hydroxyethyl group i-is converted to a colorations.

It will be understood that in all of the examples wherein a phosphoricacid ester com- '-cmoHz-'o-P== 4N pound is formed, the correspondingthiophos- I 7 CH! phoric acid ester compounds can be prepared by l e l lI p using an equivalent amount of the thi'ophosgroup The dyecompoundobtainedcdlors celluph'ori'c fphosphatin'g agent correspondingto the -l0se acetate silk'red- V phosphoric rph'osphating J-ag'entemployed. Bimilarly, in those examples where a phosphorus phosphatingagent is employed a thiophosphoric or phosphoric phosphating agentcorresponding thereto can be employed to obtain dye compounds of ourinvention.

In certain of the examples'ithe phosphorus group is shown'in a salt formthe preparation of which is not described.-. From the descriptionwhich'has been given'the preparation of the particular salt 'form shownor other salt forms will "be apparent, The free'acid'form of thecompounds of our invention can be prepared by treat ing the salt forms"with a mineralacidsuch'as hydrochloricacid. V i a It isto'be understoodthat the term anjalkyl group includes unsubstituted alky-lgfoups such asmethyl,ethyl, propyl and butyl as well as substituted alkyl groups suchas p-hydroxyethyl', phydroxypropyl, 'y-hydroxypropyl, p,'y;dihydroxypropyl, p-methoxy ethyl and p-ethoxy ethyl, for example.Similarly-the term an amino group 7 includes the amino group as well assubstituted a inofgm'ups' s fc as methyla m eth m no, *pro'pylamino;fl-hydroxyethylami'n'o; 'gly'ce'rylamino and pi-methoxy ethylaminc, forexample.

Numerous phosphating agents can be employed in: the preparation of thecompounds of our invention. :The preparation. of, a large :number ofphosphating agents which we can employ i g-iven hereinafter. 7 1

Phosphating agents having ,the formula:

wherein A and B each represents a halogen atom and X represents anamino, an O-alkyl; an'O- aryl, an O-cycloalkyl, an O-aralkyl or anO-furyl with ammonia;

"-"Phosphating compounds havin the vgeneml formula; H

.. "-Onz V wherein Y represents hydrogen or an alkyl groupmaybepreparedby reacting in equal molar pro- '-portions', phosphorusoxychloride withja compound havingthe general formula awhereinrY.represents hydrogen or iijfaikyrgriip. .Phosphorus.Ioxychloride;can;be-reacted;f rJeX- 515 The chloroform may be removedbydistillation' aaamas gample, 1 with;v ammonia, methylarnine;ethylamine, dimethylamine and.ethanolamine to obtain clohexanol andbenzyl alcohol fOl a hydroxyaryl compound, compounds wherein Z is alkyl,cycloalkyl or aralkyl can likewise be prepared. Further, by thesubstitution of phosphorus sulfochloride for phosphorus oxychloride, the'corre-'' sponding thiophosphoric compounds can be prear e The generalmethod of preparing the phosphating agents will be further clarified bythe following examples: I Preparation of;

v H V 16 grams or phosphorus ,oxychloride are dissolvdin'lbfl'gramslofpyridine and the resultiifg solution is cobled'to 0C. 45gramsof dimethylamine dissolved in 50 cc. of cold dry pyridine are thenadded with stirring and stirring is continued until reaction iscomplete. The desired compound may be recovered by fractionaldistillation of the reaction mixture under reduced pressure. i v

Preparation of phenom phosphorus orydichloiide 47 grams of 'phenoi, 154grams'of phosphorus oxychloride, and 7.5 grams of magnesium chloride aremixed together and heated on a steam bath for 8 hours, following whichthe reaction mixture is heated to 1101120 C. for 2 hours. The reactionmixture'is'then' fractionatedunderreduced pressure to give a good yieldof phenoxy phosphorus oxydichlorideboiling at -l05/3 mm. Phosphorussulfoch'loride. can be substituted for phosphorus oxychloride in theabove reaction to prepare phenoxy phosphorus sulfodichloride.Otherhydroxy aromatic. compounds canbe substituted' "for phenol in 'the;abo eureaction j to. ob-

tain various aromatic 01oz phosphorus chlorides. V

Preparati0n of amylomy Y 85 grams of phosphorus sulfodichloride in 50' 7cc. of chloroform are added to 44 grams of amyl' alcohol in cc. ofchloroform and the reaction mixture .isheated .On'FQ steam ba ionu underreduced pressure to obtain amyloxy phosmaterial or materials undergoingcoloration, phorus sulfddichloride. By the use of 88 grams Dispensing orsolubilizing'agents that can beemof amyl alcohol, diamyloxy phosphorussulfoplayed for preparing suspensions of the relatively'monochloride.cansbeobtained. Similarly, by the insoluble dye compoundinclude v soap, sulfouse of phosphorus oxych'loride the correspondingricinoleic acid, Ea salt of sulforicinoleic acid and phosphorusoxychlorides can be prepared. Again, sulfonated oleic, stearidor,palmitic acid or salts by .the use of an alcoholflnther than amyl, otherthereof such, for instance, as thesodiumoram- Phosphorus su'lfochloridecompounds can be'p tsh V I I 1, ifr. j v pared. To illustrate, it ethylalcohol is used, The following example illustrates howidyeing ethoxyphosphorus sulfodichloride and diethoxy y be Carried Out in a ordancewith our invenphosphorus sulfomonochloride can be prepared. tion.Quantities are expressed in parts by Preparation of ethylaminophosphorus oxy- Welght" Exam e A dichloride I 2.5 parts of the dyecompoundof Example 1 are 53 grams of ethylamme hydrochloride heatedadded to 834 parts of water heated to 45-55 0.

W 200 grams of Phosphorus oxychlonde and and 100 parts of celluloseacetate in the form of he mixture is refluxed foul hours Any threads-orfibers or fabric, for example, are en- 0888 phosphorus oxycmoride f beremoved by tered and the temperature raised to 80-85 C.

distillation The product obtained h the The cellulose acetate .is workedat this temperamul l a ture until dyeing is complete. The cellulose 01acetate is dyed a blue shade of good light fastness.

EL Where an insoluble or relatively insoluble dye 1I\ compoundpflourinvention is @employed' as the 0 C1 dye,- it'will, as previously-meted,be fiISt'.Sl1b- In place of et yl a y i a y o Seflmdary jected to adispersing or solubilizing treatment alkylamine may be used andin placeof ph following which the dyeing operation may be caroxychloride, posphorus sulfochlide y be ried out in accordance with the general methodused. If .n-propylamine hyd e E 5 9- described above.

stituted for ethylaminehydrochloride above, for While ,ourinventionhasbeen. illustrated inconexample,n-propy n n p u r 3 nection withthedyeingof cellulose acetate silk, can be obtained. Similarly, if PS0]: issubstituted t i l beunderstood that dyeing operations can for phosphorusoxychloride, ethylaminODhosbe carried out in a manner similar to-thatdephorus sulfodichloride will be obtained. scribed above by thesubstitution of another or- Th indigoid dye compounds of .our inventionganic derivative of cellulosematerial or another re, for the mosbpart,50111516 in W r n m y of the materials named herein for the cellulose beapplied to material underg dy m a acetate silk or by employing a dyecompound aqueous solution of the dye. Those compounds other thanthatemployed in the example. or by which are relatively insoluble orsufficiently insubstitution of both the material being dyed and solublein water as to render the use of a disthe dye compound of the example.persing or solubilizing agent advantageous may be We claim: l employedfor the direct dyeing of the materials 1. The indigo'compoundvhaving inits sodium named herein by grinding the dye to a fine pow salt form theformula:

0 moo P; 0on3 \.POH2CH2C- -r r-orncrnor o ,1 e 33m g oom NCHzCHzOP H r 0ONa der, intimately mixing it with a suitable dispers- 2. An indigoidcoloring compound having'the ing or solubilizing agent and adding theresulting formula: mixture to water or a dilute solution of soap in 0 0water to form an aqueous dyebath. Following l H this known preparationof the dyebath, the material or materials to be dyed (ordinarily textileC=O materials) may be added to the dyebath and the dyeing operationconducted in known fashion. N If desired, common salt may be added topromote H H exhaustion of the dyebath. wherein X and X1 each representsa low carbon Dyeing operations can be conducted advantaaliphatic p, Yand 1 e c represents a geously at a temperature of 80-85 C. but any berselected from the group consisting of a suitable temperature may beemployed. In ac- O. ]k 1 O a1ky1 omkyl cordance with the usual dyeingpractice, the ma- 0 terial or materials to be dyed will ordinarily be aand a added to the dyebath at a temperature lower than R1 1 R1 that atwhich the main portion of the dyei g is group wherein R1 represents amember selected tobe effected. A temperature approximating from th groupconsisting f a o and a 45-55" 0., for example, following which the tem-R perature of the dyebath is raised to that selected for carrying outthe dyeing operation. The temperature at which the dyeing is conductedwill R6 vary somewhat depending upon the particular group wherein R3represents a member selected from the group consisting of hydrogem asalt forming group, an alkyl group, an aryl group, a furyl group, acycloalkyl group and an aralkyl group and R4 and R5 each represents amember selected from the group consisting of hydrogen and an alkyl groupand wherein Y1 may be in addition hydrogen. 7 A V v 3, An indigoidcoloring compound having the formula: J t

-, i O. O a

V g ,g -t Y H H a Yl-CHflCHiN N-omom-Y N H H wherein Y and Y1eachrepresents a member selected from the group consisting of a groupwherein R1 represents a member selected from the group consisting ofr a-OR3 and a 1 s group wherein R2 represents a member selected fromthegroup consisting of hydrogen, a salt forming group, an alkyl group,an aryl group, a'

furyl group a. 'cycloalkyl group and an aralkyl group and R4 and R5 eachrepresents a member selected from'the group consisting of hydrogen andanalkyl group and wherein Y1 may be in addition hydrogen. a 1

V 4. The indigoid compound having the formula:

" o a o r 01310013301120 1) OH-NHJCHaCHaOH 5. An'indigoid coloringcompound haying the formula:

7 I 1 j C wherein X and X1 each represents a low carbon aliphatic group,Z and Z1 each represents a member' selected from the group consisting ofan -NH-group, and -O- atom and an S- atom, Q and Q1 each represents amember selected from the group consisting of an NH- group and an -'S-'atom, Y and Y1 each represents a member selectedlfrom the groupconsisting of a 1 I o-alkyl O-alkyl "-O-P a -o 'r=o a anda O-alkyl-o'-P=s group, wherein R1 representsa member selected from the groupconsisting of OR:; and a group wherein Rarepresents a member selectedNH-CH -CH;

OHaOCHaCHaO A) OH-NHzCHgOHzOH JOSEPH B. DICKEY. JAMES G. McNALLY.

